CN105664241A - Production method for mechanical property controllable polyvinyl alcohol cartilage stents - Google Patents
Production method for mechanical property controllable polyvinyl alcohol cartilage stents Download PDFInfo
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/06—Materials or treatment for tissue regeneration for cartilage reconstruction, e.g. meniscus
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Abstract
The invention provides a production method for mechanical property controllable polyvinyl alcohol cartilage stents.According to the method, a numerical computation method of molecular dynamics is utilized for modeling of a PVA hydrogel system, the system is subjected to molecular dynamics equilibrium calculation from the level of micromolecular interaction, and micro static mechanics property parameters of the hydrogel system are obtained.Further, material properties can be predicted, theoretical calculation results and actual demands are combined, the mass ratio of PVA to deionized water is regulated, the mass ratio in conformity with the requirements of elasticity modulus is found finally, and accordingly reliable technical parameters are provided for production of the cartilage stents, the cartilage stents with specific elasticity modulus can be produced quickly and simply, and the development cycle of cartilage stent materials is shortened greatly.
Description
Technical field
The present invention relates to the preparation method of a kind of PVA cartilage frame. Relating to take molecular dynamics as the theory of computation, is calculated the micromechanics of polyvinyl alcohol (PVA) Blend hydrogel body material by numerical simulation, thus realizes controlled to PVA cartilage frame mechanical property.
Background technology
The cartilage defect caused due to disease, aging, accident and war etc. is common in media and clinical case, particularly for athletes, cartilage defect very likely causes its sportsmen's career terminating oneself too early, and serious more may impact the orthobiosis that it is later. Therefore repair of cartilage problem is very urgent, and solving this most effective method of problem of cartilage defect is that defect cartilage position is carried out artificial substituting. But the regeneration of cartilage is face an one big difficult problem, and current clinical main periosteum, non-degradable or degradable biological material are repaired, but the defect that these methods for the treatment of have it intrinsic. If degraded product is to the untoward reaction of body, nondegradable material causes the rejection of body and long-term effect not to get well. Being mostly of current application utilizes macromolecular material support transmission chondrocyte to repair cartilage defect, but medical macromolecular materials are expensive and tissue is had destructiveness by its degraded product, so, the preparation of cartilage frame is generally by bioengineered tissue employing hydrogel material. And the use of polyvinyl alcohol (PVA) hydrogel is the most extensive, because PVA hydrogel is except possessing the performance of general hydrogel, have that toxicity is low, mechanical property is excellent (high elastic coefficient and high physical strength) especially, the advantage such as water regain height and good biocompatibility, as medical treatment substitute material, there is potential application prospect. PVA class hydrogel has been carried out comparatively deep research by a lot of scientific research personnel, and achieves great successes.
The cartilage frame of clinical upper use must meet certain mechanical property, because cartilage is generally distributed in the joint part of human body, carries certain load, and different joint parts is to different to the mechanical property requirements of cartilage. In addition, different sufferers is also different to the mechanical property requirements of cartilage frame at same joint part. Its mechanical property of desirable cartilage frame must be mated mutually with the individual specificity of sufferer, and our manufacturing process is just proposed challenge by this.How to prepare the difficult problem that the cartilage frame to have certain force performance becomes cartilage frame preparation technology, traditional method can only be by constantly testing trial, then sample is carried out test and could prepare the cartilage frame to have certain force performance, not only cost is higher for this process, and the construction cycle is longer, it is unfavorable for reparation, the treatment of sufferer cartilage.
Summary of the invention
In order to overcome the uncontrollable problem of cartilage frame mechanical property in tradition preparation technology, the present invention proposes the preparation method of the controlled polyvinyl alcohol cartilage frame of a kind of mechanical property, utilize the numerical evaluation method of molecular dynamics, by PVA aquogel system is carried out modeling, system is carried out molecular dynamics EQUILIBRIUM CALCULATION FOR PROCESS by the aspect interacted from micro molecule, and obtains the microcosmic static mechanical property parameter of aquogel system. And then the character of material can be predicted, for the preparation of cartilage frame provides reliable processing parameter, the cartilage frame body material according to individual difference customization with different physical strength can be obtained quickly and easily, substantially reduce the R&D cycle of cartilage support material, for sufferer prepares the cartilage frame that mechanical property mates mutually fast.
The technical scheme of the present invention is:
The preparation method of the polyvinyl alcohol cartilage frame that described a kind of mechanical property is controlled, it is characterised in that: comprise the following steps:
Step 1: built high-molecular polyvinyl alcohol chain model and water molecules model by molecular dynamics simulation simulation software respectively, the mass ratio that the high-molecular polyvinyl alcohol chain built and water molecules are pressed M:N builds the nothing sizing structure cell model of polyvinyl alcohol hydrogel system;
Step 2: set up the force field without sizing structure cell model being applicable to step 1 gained polyvinyl alcohol hydrogel system in molecular dynamics simulation simulation software; And under force field, the nothing sizing structure cell model of polyvinyl alcohol hydrogel system is carried out molecular dynamics emulation; After polyvinyl alcohol hydrogel system balances, then polyvinyl alcohol hydrogel trimming trajectory is carried out static mechanical property analysis, obtain the mechanical property of polyvinyl alcohol hydrogel system;
Step 3: according to sufferer to the requirement of cartilage frame mechanical property, and the mechanical property of polyvinyl alcohol hydrogel system that step 2 obtains, adjustment builds polyvinyl alcohol hydrogel system without the high-molecular polyvinyl alcohol chain of structure cell model and the mass ratio of water molecules of shaping, repeating step 2 again, until the mechanical property of polyvinyl alcohol hydrogel system reaches sufferer to the requirement of cartilage frame mechanical property, obtain the mass ratio m:n of now high-molecular polyvinyl alcohol chain and water molecules;
Step 4: calculate the high-molecular polyvinyl alcohol chain of gained and the mass ratio m:n of water molecules according to step 3, take Polymers of Polyvinyl Alcohol and the deionized water of respective quality;
Step 5: the Polymers of Polyvinyl Alcohol taken is mixed with deionized water and at room temperature stirs evenly, then put into 90 DEG C of water bath with thermostatic control environment; After Polymers of Polyvinyl Alcohol is dissolved completely, the container that polyvinyl alcohol water solution is housed is taken out from water bath, and constant temperature de-soak under being placed in 40 DEG C～70 DEG C environment;
Step 6: after the polyvinyl alcohol water solution of step 5 gained is clarified, this polyvinyl alcohol water solution is poured in the medical mould with sufferer cartilage frame outward appearance shape, then together with mould carry out multiple freezing-thaw cycles process, obtain polyvinyl alcohol cartilage frame;Single freezing-treating processes of thawing is: by mould that polyvinyl alcohol water solution is housed under not higher than-15 DEG C of environment freezing at least 10 hours, and then thaw at least 6 hours under being placed in 25 DEG C～30 DEG C environment.
Further preferred version, the preparation method of the polyvinyl alcohol cartilage frame that described a kind of mechanical property is controlled, it is characterised in that: step 5 and step 6 are preferably:
Step 5: the Polymers of Polyvinyl Alcohol taken is mixed with deionized water and at room temperature stirs evenly, then put into 90 DEG C of water bath with thermostatic control environment; After Polymers of Polyvinyl Alcohol is dissolved completely, the container that polyvinyl alcohol water solution is housed is taken out from water bath, and constant temperature de-soak under being placed in 60 DEG C of environment;
Step 6: after the polyvinyl alcohol water solution of step 5 gained is clarified, this polyvinyl alcohol water solution is poured in the medical mould with sufferer cartilage frame outward appearance shape, then carry out 5 freezing-thaw cycles process together with mould, obtain polyvinyl alcohol cartilage frame; Single freezing-treating processes of thawing is: the mould under-20 DEG C of environment freezing 16 hours that polyvinyl alcohol water solution will be housed, and then thaw 6 hours under being placed in 25 DEG C of water bath with thermostatic control environment.
Useful effect
The invention has the beneficial effects as follows:
(1) Young's modulus of artificial bone matrix material is studied by the present invention from material micro molecule aspect, it is to increase cartilage support material physical strength assess effectiveness, and the bone support based theoretical for the corresponding mechanical property of customization.
(2) the present invention is theoretical based on Molecular Dynamics Calculation, numerical evaluation method by platform of molecular dynamics software, can according to sufferer to the requirement of the specific mechanical property of cartilage frame, quickly and efficiently the model of PVA hydrogel is built, and obtain corresponding mechanical property, for the preparation of PVA cartilage frame provides reliable technique reference. The processing method that this kind of targeted is clear and definite substantially reduces the preparation time of PVA cartilage frame.
(3) patent of the present invention is by numerical evaluation method, PVA hydrogel cartilage frame is prepared by changing the mass ratio of PVA and deionized water, not only low production cost, operating procedure are easy, the cartilage frame body material can with specific mechanical strength simultaneously, thus ensured the reliability of the mechanical property of cartilage frame.
Accompanying drawing explanation
Fig. 1 is the Molecular Dynamics Calculation model of PVA aquogel system.
Embodiment
Below in conjunction with specific embodiment, the present invention is described:
Embodiment 1:
The polymerization degree of the PVA macromolecular material selected in the present embodiment is 1750 ± 50, and water is deionized water. The preparation method of the polyvinyl alcohol cartilage frame that concrete a kind of mechanical property is controlled comprises the following steps:
Step 1: build high-molecular polyvinyl alcohol chain model and water molecules model respectively by molecular dynamics simulation simulation software (materialstudios software), wherein built polyvinyl alcohol molecular chain is 50 containing repeating unit body number, and the mass ratio that the high-molecular polyvinyl alcohol chain built and water molecules are pressed M:N builds the nothing sizing structure cell model of polyvinyl alcohol hydrogel system. In the present embodiment, M:N gets 25:75, is built containing 4 PVA macromolecular chains in structure cell model, 1221 water moleculess.
Step 2: in molecular dynamics simulation simulation software, sets up the force field without sizing structure cell model being applicable to step 1 gained polyvinyl alcohol hydrogel system by script file editor;And under force field, the nothing sizing structure cell model of polyvinyl alcohol hydrogel system is carried out molecular dynamics emulation:
First carrying out the Molecular Dynamics Calculation of 50ps under isothermal and isobaric (NPT) assemblage, the final mask then NPT assemblage Molecular Dynamics Calculation obtained carries out the Molecular Dynamics Calculation of 80ps under (constant temperature perseverance is held) NVT assemblage.
After polyvinyl alcohol hydrogel system balances, then polyvinyl alcohol hydrogel trimming trajectory is carried out static mechanical property analysis, obtain the mechanical property of polyvinyl alcohol hydrogel system: the Young's modulus paying close attention to polyvinyl alcohol hydrogel system here is 5.86Gpa.
Step 3: according to sufferer to the requirement (Young's modulus 6.75GPa) of cartilage frame mechanical property, and the mechanical property (Young's modulus is 5.86Gpa) of polyvinyl alcohol hydrogel system that step 2 obtains, adjustment builds the mass ratio of the high-molecular polyvinyl alcohol chain of polyvinyl alcohol hydrogel system without sizing structure cell model and water molecules. Now, the mechanical property of institute's established model is less than actual demand, therefore reduces the water molecules in model then repeating step 2; By constantly adjusting the ratio of component of PVA aquogel system, corresponding system is carried out mechanical property calculating, until the mechanical property of polyvinyl alcohol hydrogel system reaches sufferer to the requirement of cartilage frame mechanical property, obtain the mass ratio m:n of now high-molecular polyvinyl alcohol chain and water molecules, the m:n that the present embodiment obtains is 30:70, and computation model contained humidity number is 1140.
Step 4: calculate the high-molecular polyvinyl alcohol chain of gained and the mass ratio m:n of water molecules according to step 3, take Polymers of Polyvinyl Alcohol and the deionized water of respective quality; Namely the present embodiment takes 15gPVA, 35g deionized water respectively.
Step 5: the Polymers of Polyvinyl Alcohol taken and deionized water are put into and mixes in beaker and at room temperature stir evenly, then put into 90 DEG C of thermostat water baths; After Polymers of Polyvinyl Alcohol is dissolved completely, the beaker that polyvinyl alcohol water solution is housed is taken out from water-bath, and it is placed in 60 DEG C of baking oven constant temperature de-soaks.
Step 6: after the polyvinyl alcohol water solution of step 5 gained is clarified, this polyvinyl alcohol water solution is poured in the medical mould with sufferer cartilage frame outward appearance shape, then carry out 5 freezing-thaw cycles process together with mould, obtain polyvinyl alcohol cartilage frame; Single time freezing-treating processes of thawing is: the mould under-20 DEG C of environment freezing 16 hours that polyvinyl alcohol water solution will be housed, and then thaws 6 hours under being placed in 25 DEG C of water bath with thermostatic control environment.
The PVA cartilage frame of gained being carried out Mechanics Performance Testing, and show that observed value now is 6.26GPa, this result and theoretical value are more or less the same, in the scope that can accept.
Embodiment 2:
In this embodiment, concrete implementation step and example 1 the difference is that moisture molecule number in step 3 final institute established model be 1960, PVA macromolecular chain is 4, and the experiment material PVA of record and deionized water quality are 20:80 than m:n, and the calculated value of institute's established model Young's modulus is 4.96GPa. And to prepare the PVA that cartilage frame takes be 10g, deionized water 40g, and made cartilage frame Young's modulus experiment test result is 4.48GPa, this result and theoretical value are more or less the same, in the scope that can accept.
Embodiment 3:
In this embodiment, concrete implementation step and example 1 the difference is that moisture molecule number in step 3 final institute established model be 3300, PVA macromolecular chain is 3, and the experiment material PVA of record and deionized water quality are 10:90 than m:n, and the calculated value of institute's established model Young's modulus is 3.78GPa.And to prepare the PVA that cartilage frame takes be 5g, deionized water 45g, and made cartilage frame Young's modulus experiment test result is 3.39GPa, this result and theoretical value are more or less the same, in the scope that can accept.
Embodiment 4:
In this embodiment, concrete implementation step and example 1 the difference is that moisture molecule number in step 3 final institute established model be 4650, PVA macromolecular chain is 2, and the experiment material PVA of record and deionized water quality are 5:95 than m:n, and the calculated value of institute's established model Young's modulus is 3.01GPa. And to prepare the PVA that cartilage frame takes be 2.5g, deionized water 47.5g, and made cartilage frame Young's modulus experiment test result is 2.92GPa, this result and theoretical value are more or less the same, in the scope that can accept.
The experimental data of above-mentioned four embodiments is in table 1.
Table 1 different components is than the numerical evaluation of PVA hydrogel cartilage rack elasticity modulus and experiment test result
Although above it has been shown and described that embodiments of the invention, it is understandable that, above-described embodiment is exemplary, can not being interpreted as limitation of the present invention, above-described embodiment can be changed when not departing from principle and the objective of the present invention, revises, replace and modification by the those of ordinary skill of this area within the scope of the invention.
Claims (2)
1. the preparation method of the polyvinyl alcohol cartilage frame that a mechanical property is controlled, it is characterised in that: comprise the following steps:
Step 1: built high-molecular polyvinyl alcohol chain model and water molecules model by molecular dynamics simulation simulation software respectively, the mass ratio that the high-molecular polyvinyl alcohol chain built and water molecules are pressed M:N builds the nothing sizing structure cell model of polyvinyl alcohol hydrogel system;
Step 2: set up the force field without sizing structure cell model being applicable to step 1 gained polyvinyl alcohol hydrogel system in molecular dynamics simulation simulation software; And under force field, the nothing sizing structure cell model of polyvinyl alcohol hydrogel system is carried out molecular dynamics emulation; After polyvinyl alcohol hydrogel system balances, then polyvinyl alcohol hydrogel trimming trajectory is carried out static mechanical property analysis, obtain the mechanical property of polyvinyl alcohol hydrogel system;
Step 3: according to sufferer to the requirement of cartilage frame mechanical property, and the mechanical property of polyvinyl alcohol hydrogel system that step 2 obtains, adjustment builds polyvinyl alcohol hydrogel system without the high-molecular polyvinyl alcohol chain of structure cell model and the mass ratio of water molecules of shaping, repeating step 2 again, until the mechanical property of polyvinyl alcohol hydrogel system reaches sufferer to the requirement of cartilage frame mechanical property, obtain the mass ratio m:n of now high-molecular polyvinyl alcohol chain and water molecules;
Step 4: calculate the high-molecular polyvinyl alcohol chain of gained and the mass ratio m:n of water molecules according to step 3, take Polymers of Polyvinyl Alcohol and the deionized water of respective quality;
Step 5: the Polymers of Polyvinyl Alcohol taken is mixed with deionized water and at room temperature stirs evenly, then put into 90 DEG C of water bath with thermostatic control environment; After Polymers of Polyvinyl Alcohol is dissolved completely, the container that polyvinyl alcohol water solution is housed is taken out from water bath, and constant temperature de-soak under being placed in 40 DEG C～70 DEG C environment;
Step 6: after the polyvinyl alcohol water solution of step 5 gained is clarified, this polyvinyl alcohol water solution is poured in the medical mould with sufferer cartilage frame outward appearance shape, then together with mould carry out multiple freezing-thaw cycles process, obtain polyvinyl alcohol cartilage frame;Single freezing-treating processes of thawing is: by mould that polyvinyl alcohol water solution is housed under not higher than-15 DEG C of environment freezing at least 10 hours, and then thaw at least 6 hours under being placed in 25 DEG C～30 DEG C environment.
2. the preparation method of the polyvinyl alcohol cartilage frame that a kind of mechanical property is controlled according to claim 1, it is characterised in that: step 5 and step 6 are preferably:
Step 5: the Polymers of Polyvinyl Alcohol taken is mixed with deionized water and at room temperature stirs evenly, then put into 90 DEG C of water bath with thermostatic control environment; After Polymers of Polyvinyl Alcohol is dissolved completely, the container that polyvinyl alcohol water solution is housed is taken out from water bath, and constant temperature de-soak under being placed in 60 DEG C of environment;
Step 6: after the polyvinyl alcohol water solution of step 5 gained is clarified, this polyvinyl alcohol water solution is poured in the medical mould with sufferer cartilage frame outward appearance shape, then carry out 5 freezing-thaw cycles process together with mould, obtain polyvinyl alcohol cartilage frame; Single freezing-treating processes of thawing is: the mould under-20 DEG C of environment freezing 16 hours that polyvinyl alcohol water solution will be housed, and then thaw 6 hours under being placed in 25 DEG C of water bath with thermostatic control environment.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108310469A (en) * | 2018-01-25 | 2018-07-24 | 四川大学 | A kind of preparation method of high-performance polyethylene alcohol hydrogel artificial cartilage replacement material |
| CN108334737A (en) * | 2017-01-20 | 2018-07-27 | 中国石油化工股份有限公司 | A kind of demulsifier selection method based on molecular simulation |
| CN108715641A (en) * | 2018-05-25 | 2018-10-30 | 湖州斯蔓生物材料有限公司 | PVA hydrogels use its composite material, its manufacturing method and its application |
| CN111790327A (en) * | 2019-04-09 | 2020-10-20 | 中国科学院化学研究所 | Molecular design method of ice control material |
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| CN103120806A (en) * | 2013-01-16 | 2013-05-29 | 西北工业大学 | Preparation method of cartilage framework based on PVA (Polyvinyl Acetate) hydrogel |
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| US20070213453A1 (en) * | 2004-08-25 | 2007-09-13 | Rolf Muller | Polyvinyl alcohol gels, especially in situ gelling gels |
| CN102283723A (en) * | 2011-06-09 | 2011-12-21 | 西北工业大学 | Method for quickly molding biological ceramic microsphere artificial bone scaffold with controllable mechanical property |
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| CN108715641A (en) * | 2018-05-25 | 2018-10-30 | 湖州斯蔓生物材料有限公司 | PVA hydrogels use its composite material, its manufacturing method and its application |
| CN111790327A (en) * | 2019-04-09 | 2020-10-20 | 中国科学院化学研究所 | Molecular design method of ice control material |
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